EP1525247A2 - Komplexbildner f r die behandlung von metall- und kunststoff oberfl chen - Google Patents

Komplexbildner f r die behandlung von metall- und kunststoff oberfl chen

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Publication number
EP1525247A2
EP1525247A2 EP03760658A EP03760658A EP1525247A2 EP 1525247 A2 EP1525247 A2 EP 1525247A2 EP 03760658 A EP03760658 A EP 03760658A EP 03760658 A EP03760658 A EP 03760658A EP 1525247 A2 EP1525247 A2 EP 1525247A2
Authority
EP
European Patent Office
Prior art keywords
metal
component
acid
polymer
metals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03760658A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ralf Friedrich
Werner Hesse
Hans-Ulrich JÄGER
Helmut Witteler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1525247A2 publication Critical patent/EP1525247A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating

Definitions

  • the invention relates to compositions for the surface treatment of metals, methods for the surface treatment of metals, the use of polymers for the surface treatment of metals.
  • the invention further relates to a composition and a method and the use of polymers for the deposition of metals or metal alloys on metal and plastic surfaces.
  • Formulations containing complexing agents for metal cations are used in chemical and electrochemical metal deposition on metals or plastics and in the surface treatment of metals.
  • No. 6,284,309 relates to a method for producing a surface which is suitable for forming a co-continuous bond.
  • the process includes the following steps:
  • etching composition which contains the following components ba) an acid bb) an oxidizing agent bc) a complexing agent for copper, which is selected from the group consisting of thioureas and imidazole Thions, and bd) a copper complex, in an amount in which it fails when applied to the copper or copper alloy substrate.
  • the amount of complexing agent in the etching composition is 0.5 to 20% by weight.
  • US 6,197,181 relates to a method for applying a metallic contact to a semiconductor surface.
  • the method includes forming an ultra-thin metal seed layer on a barrier layer applied to the semiconductor surface.
  • This ultra-thin layer can be reinforced by depositing additional metal on it. Copper is preferably used as a further metal.
  • the deposition is particularly preferably carried out electrochemically in an alkaline bath. In this bath, complexing agents selected from the group consisting of EDTA (ethylenediaminetetraacetic acid), ED (ethylenediamine) and polycarboxylic acids, in particular citric acid, or salts thereof are used as complexing agents.
  • EDTA ethylenediaminetetraacetic acid
  • ED ethylenediamine
  • polycarboxylic acids in particular citric acid, or salts thereof are used as complexing agents.
  • the complexing agents used in the prior art in formulations for metal deposition or for surface treatment of metals have the disadvantage that they cause ecological problems in their disposal. Complexing agents that get into the wastewater are problematic because they make heavy metals bioavailable.
  • the object of the present invention is therefore to provide complexing agents for formulations for the deposition of metals on metal or plastic surfaces and for formulations for the surface treatment of metals which are ecologically harmless.
  • composition for the treatment of metal or plastic surfaces comprising a) at least one polymer as component A containing at least one structural unit of the formula (I)
  • this structural unit can be part of a polymer main chain or can be bonded to a polymer main chain via an anchor group, and M is hydrogen or an ammonium or metal cation;
  • component C optionally surface-active compounds, dispersants, suspending agents and / or emulsifiers as component C; either d) optionally a salt, an acid or a base based on transition metal cations, transition metal oxo anions, fluorometalates or lantanoids as component D, and / or
  • component F at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, sulfonic acids, nitric acid, hydrofluoric acid and hydrochloric acid as component E, or a base selected from the group consisting of alkali and alkaline earth metal hydroxides and ammonia solution or f) at least one metal oxide and / or metal salt as component F.
  • the main polymer chain is to be understood as the longest chain forming the polymer.
  • This chain is made up of carbon atoms lined up by covalent bonds, although this carbon chain can be interrupted by heteroatoms, in particular nitrogen, silicon or oxygen.
  • this chain can have branches which are also made up of carbon atoms and optionally nitrogen and oxygen atoms.
  • An anchor group is to be understood as a group which links the structural unit of the formula (I) to the main polymer chain.
  • Such anchor groups can be alkylene groups with 1 to 14 carbon atoms, which can be interrupted by heteroatoms, in particular nitrogen or oxygen. These anchor groups can be attached to carbon atoms or to heteroatoms in the main polymer chain.
  • the polymers used according to the invention are outstandingly suitable as complexing agents in the compositions for the treatment of metal surfaces and also in compositions for the deposition of metals on metal or plastic surfaces.
  • component A the polymers used according to the invention
  • the polymers precipitate out quantitatively or are surface-absorbed. This behavior is also known as bioelimination and is assessed by the specialist in an ecologically favorable manner.
  • the polymers (component A) used according to the invention increase the stability of the compositions, in particular baths for chemical metal deposition.
  • the composition according to the invention can be used in all processes for metal treatment or for the deposition of metals on plastic surfaces.
  • compositions containing components A, B, optionally C and D and / or (instead of D) E are particularly suitable for surface treatment of metals, while compositions containing components A, B, optionally C and F are particularly suitable for the deposition of metals or metal alloys suitable on metal or plastic surfaces.
  • Such processes are, for example, the passivation, in particular phosphating, of metal surfaces, preferably chromate-free, the pickling of metal surfaces, the sealing of metal surfaces and the metal deposition on metal surfaces, for example by nickel plating, galvanizing, tinning, copper plating or alloy deposition.
  • the compositions can be used to produce paints or rust converters.
  • the compositions according to the invention can be used to deposit metals on plastic surfaces, for example in the manufacture of printed circuit boards.
  • Suitable metal surfaces are generally technically customary materials selected from the group consisting of aluminum and magnesium alloys, steel, copper, zinc, tin, nickel, chromium and technically customary alloys of these metals.
  • Other suitable metal surfaces are precious metals, especially gold and silver and their alloys.
  • metal coatings which can be produced chemically or electrochemically, selected from the group consisting of zinc and its alloys, preferably metallic zinc, zinc / iron, zinc / nickel, zinc / manganese or zinc / cobalt - Alloys, tin and its alloys, preferably metallic tin, tin alloys containing Cu, Sb, Pb, Ag, Bi and Zn, particularly preferably those which are used as solders, for example in the manufacture and processing of printed circuit boards, and Copper is preferred in the form in which it is used on printed circuit boards and metallized plastic parts.
  • zinc and its alloys preferably metallic zinc, zinc / iron, zinc / nickel, zinc / manganese or zinc / cobalt - Alloys, tin and its alloys, preferably metallic tin, tin alloys containing Cu, Sb, Pb, Ag, Bi and Zn, particularly preferably those which are used as solders, for example in the manufacture and processing of printed circuit boards, and Copper is preferred in the form
  • compositions according to the invention are used for pickling or passivating, in particular phosphating, metal surfaces
  • metal surfaces are made of steel, cast iron, zinc, aluminum, magnesium and or alloys of these metals preferred with each other or with other alloy components. In these cases, zinc and aluminum and alloys of these metals with other alloy components are particularly preferred.
  • compositions according to the invention are used for the deposition of metals on metal surfaces
  • steel surfaces are preferred for the galvanizing and deposition of zinc alloys as well as for the coppering and nickel plating and copper and steel for the tinning (also Sn alloys).
  • composition according to the invention for the treatment of metal surfaces which have not been pretreated. However, it is preferred that the metal surfaces have been cleaned at least before treatment with the composition according to the invention.
  • the cleaning preferably includes degreasing the metal surface. Suitable cleaning or degreasing processes are known to the person skilled in the art. It is also possible to use the composition according to the invention in a process step following pickling or passivation of the metal surface, for example in a painting step.
  • the compositions according to the invention can also be used as cleaning, pickling and polishing formulations which contain additives known to the person skilled in the art and can be used in corresponding processes.
  • compositions according to the invention can also be used to deposit metals or metal alloys on plastic surfaces.
  • Compositions which are suitable for nickel-plating and copper-plating of plastic surfaces are preferred, for example for copper-plating in the production of printed circuit boards.
  • the plastic surfaces are prepared for metallization using standard technical processes.
  • the compositions according to the invention serve to metallize the plastic, but can optionally also be used in the pretreatment for the metallization.
  • compositions are understood to mean both the ready-to-use compositions and concentrates.
  • concentrations given below for the individual components relate to the ready-to-use compositions.
  • concentrations of the individual components in concentrates are correspondingly higher.
  • Component A is a polymer containing at least one structural unit of the formula (I)
  • this structural unit can be part of a polymer main chain or can be bonded to a polymer main chain via an anchor group, and M is hydrogen or an ammonium or metal cation.
  • M is an alkali metal cation, preferably a sodium or potassium ion.
  • M is a divalent or multivalent cation, preferably an alkaline earth metal cation or Zn, Mn or Cr (III), particularly preferably magnesium or calcium.
  • the weight average molecular weight of the polymers used as component A is generally> 500 g / mol, preferably> 1000 g / mol, particularly preferably 1000-100000 g / mol.
  • the weight average was determined by means of light scattering.
  • Component A is particularly preferably polymers which have one or more repeating units of the formula (II), (EI) and or (IV), and / or one or two end groups of the formula (V), and, if appropriate, further units Formula (VI) included.
  • R is hydrogen or any substituted or unsubstituted organic radical, preferably H or radicals based on ethyleneimine such as - (CH 2 CH 2 NH) n -H
  • R * is hydrogen or -CH 2 -CO 2 M
  • M is hydrogen or an ammonium or metal cation, suitable metal cations generally being alkali metal cations, preferably sodium or potassium ions, or Ag or divalent or polyvalent cations, preferably alkaline earth metal cations or Zn, Mn or Cr (III), Ni, Fe Co, Cu,
  • the polymers used according to the invention are generally water-soluble.
  • Component A is very particularly preferably water-soluble, carboxyalkylated polymers containing amino groups. These can be obtained by reacting water-soluble polymers containing amino groups with at least one aldehyde and an alkali metal cyanide or a cyanohydrin of an aldehyde and an alkali metal cyanide in aqueous solution. Suitable water-soluble polymers containing amino groups are all water-soluble compounds which contain a basic NH group. Compounds of this type are, for example, polyalkylene polyamides. Examples include polyalkylene polyamines which have at least four basic nitrogen atoms, such as tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine and polyethylene diamines.
  • polyethyleneimines Of the polyalkylene polyamines, preference is given to polyethyleneimines. These particularly preferably have molar masses of 200 to 10,000,000, very particularly preferably 1,000 to 3,000,000 (weight average molecular weight). Polyethyleneimines with molecular weights of 2,000 to 1,300,000 are particularly preferably used.
  • modified polyethyleneimines can also be subjected to carboxyalkylation.
  • modified polyethylemmines are, for example, alkylated ones Polyethyleneimines. They are known and are prepared, for example, by reacting polyethylenimines with alkylating agents such as alkyl halides (compare US 3,251,778 and EP-B 0 379 161). Another alkylating agent is, for example, dimethyl sulfate.
  • the degree of alkylation of the polyethyleneimines is generally 1 to 50%, preferably 1 to 10%. The degree of alkylation is understood to mean the percentage of alkylated monomer units in the polymer, based on the total number of monomer units in the polyethyleneimine. Examples of suitable alkyl halides are Ci- 3 o-alkyl halides.
  • Suitable modified polyethyleneimines are reaction products of polyethyleneimines with C 2 . 22 epoxides. These reaction products are usually prepared by alkoxylation of polyethyleneimines in the presence of bases as a catalyst.
  • Sulfonated and phosphonomethylated polyemethyleneimines are also suitable. They can be produced from the polyethyleneimines by sulfonation or phosphonomethylation.
  • the carboxyalkylation is generally carried out by reacting the water-soluble polymers containing amino groups with an aldehyde, preferably formaldehyde, and an alkali metal cyanide, preferably sodium cyanide.
  • an aldehyde preferably formaldehyde
  • an alkali metal cyanide preferably sodium cyanide.
  • a cyanohydrin composed of an aldehyde and an alkali metal cyanide, for example glycol nitrite, which is formed by the addition of sodium cyanide to formaldehyde.
  • Carboxymethylated polyethyleneimines are preferably used as component A. These are preferably obtained by carboxymethylation of polyethyleneimines with formaldehyde and sodium cyanide.
  • the carboxyalkylation of the water-soluble compounds containing amino groups is preferably carried out to such an extent that 1 to 100% of the NH groups in polymers containing amino groups are carboxyalkylated.
  • the aldehyde and the alkali metal cyanide are particularly preferably used in such an amount that 75 to 100% of the NH groups in the amino group-containing polymers are carboxyalkylated.
  • the degree of preferred carboxymethylation is usually 80 to 100%, based on the NH groups in the polymer.
  • WO 97/40087 discloses processes for the preparation of the water-soluble polymers containing amino groups which are preferably used as component A, particularly preferably for the preparation of carboxyalkylated polyethyleneimines, very particularly preferably for the preparation of carboxymethylated polyethyleneimines.
  • the polymers used according to the invention as component A are in a concentration of c (A) / . c (M) from> 0.001 to ⁇ 1,000, preferably> 0.01 to ⁇ 100, particularly preferably> 0.1 to ⁇ 10.
  • c (A) means the number of carboxylate groups contained in the polymer (or
  • Treatment of metal surfaces can be brought into solution by the surface treatment of the metal M.
  • the complexing agent used in the compositions according to the invention is suitable for complexing metal cations in high concentrations.
  • the type of metal cations depends on which metals on metal or. Plastic surfaces are to be deposited, or which metals are to be subjected to a surface treatment with the compositions according to the invention.
  • Metal cations of Zn, Ni, Cu, Au, Pd, Sn, Co, Mn, Fe, Mg, Pb, Bi, Au and Ag or mixtures of these metal cations (for the deposition of alloys) are preferably complexed.
  • Component B is water or another solvent which is suitable for dissolving or dispersing, suspending or emulsifying the polymer (component A).
  • Suitable other solvents besides water are, for example, aliphatic or aromatic solvents such as benzene, toluene and xylene, halogenated solvents such as methylene chloride and chloroform, alcohols such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran, polyethers, in particular polyethylene glycol, ketones, such as Acetone, and mixtures of these solvents with one another and / or with water. Water is particularly preferably used as the solvent.
  • the pH is determined by the type of application.
  • pickling and phosphating baths are generally strongly acidic and galvanic baths are basic or acidic, depending on the type of bath.
  • Suitable pH values for the specific applications are known to the person skilled in the art.
  • the amount of water or another solvent depends on whether the composition according to the invention is a ready-to-use composition or a concentrate, and on the particular application. Basically, the amount results from the concentrations of the individual components specified for the ready-to-use composition.
  • the composition according to the invention can additionally contain surface-active compounds, emulsifiers and / or dispersants.
  • Suitable surface-active compounds are surfactants, which can be cationic, anionic, zwitterionic or nonionic.
  • Suitable surfactants are, for example, alkyl and alkenyl alkoxylates of the R-EOn / POm type, where R is generally linear or branched C 6 -C 30 -alkyl radicals, preferably C 8 -C 20 -alkyl radicals and EO for an ethylene oxide unit and PO for a Propylene oxide unit, where EO and PO can be arranged in any order and n and m are independently> 1 and ⁇ 100, preferably> 3 and ⁇ 50, for example Emulan®, Lutensol® and Plurafac® (from BASF), alkylphenol ethoxylates , EO / PO block copolymers (Pluronic®, from BASF), alkyl ether
  • the amount of these components in the composition according to the invention is generally 0.01-100 g / 1, preferably 0.1 to 20 g 1.
  • Transition metal cations are in particular fluorometalates of Ti (IV), Zr (IV), Hf (IV) and / or Si (IV), suitable lantanoids, in particular Ce. Tungsten and molybdates are also suitable.
  • compositions according to the present application are particularly suitable for either depositing a corrosion-protective layer on a metal surface or increasing the corrosion-protective effect of a corrosion layer already deposited on the metal surface.
  • the amount of component D is - if component D is contained in the compositions according to the invention - preferably 0.02 to 20 g / 1.
  • compositions according to the invention can further comprise at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, sulfonic acids such as methanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, m-nitrobenzenesulfonic acid, naphthalenesulfonic acid and derivatives thereof, nitric acid, hydrofluoric acid and hydrochloric acid.
  • E can also be a base selected from the group consisting of alkali and alkaline earth metal hydroxides and ammonia solution, in particular NaOH, KOH. The type of acid used depends on the type of treatment of the metal surface.
  • phosphoric acid is generally used in phosphating baths for phosphating steel surfaces.
  • the composition according to the invention is a phosphating solution.
  • non-layer-forming phosphating solutions which are solutions that have no divalent metals.
  • Such "non-layer-forming" phosphating solutions are, for example, in the form of an iron phosphating solution.
  • the phosphating solutions contain ions of divalent metals, e.g. B. zinc and / or manganese
  • the phosphating solutions are available as so-called "layer-forming" phosphating solutions.
  • Compositions containing nitric acid according to the present application are particularly suitable for the surface treatment of zinc and its alloys, while compositions containing hydrofluoric acid are particularly suitable for the surface treatment of aluminum and its alloys.
  • compositions is contained - 0.2 to 200 g / 1, preferably 2 to 100 g / 1, of component E.
  • Suitable metal oxides or metal salts are the oxides or salts of metals selected from the group consisting of Zn, Ni, Cu, Au, Pd, Sn, Co, Mn, Fe, Mg, Pb, Bi and Ag.
  • the metals can be deposited in the form of the metal used or - if different metals are used - in the form of alloys of the metals mentioned with one another or with other metals.
  • Preferred alloys are CuZn, CuSn, CuNi, SnPb, SnAgBiCu, SnAgCu, SnBi, SnAg, SnCu, NiPd, NiP, ZnFe, ZnNi, ZnCo and ZnMn.
  • the stated constituents of the alloys can be contained in the alloy in any concentration.
  • Zn, Cu and Ni and alloys of these metals are particularly preferably deposited with other metals or with one another.
  • Ni and Cu are particularly preferred when depositing metals or metal alloys on plastic surfaces.
  • the metals can be used as metal salts selected from the corresponding sulfates, sulfonic acid salts, chlorides, carbonates, sulfamates, fluoroborates, cyanides and acetates.
  • the concentration of the metal ions in the compositions according to the invention is generally 0.01 to 100 g / 1, preferably 0.1 to 50 g / 1, particularly preferably 2 to 20 g / 1, based on the amount of the metal used.
  • composition according to the invention is used for the surface treatment of metals and, in addition to components A, B and optionally C, and D and / or E:
  • At least one corrosion inhibitor as component G and / or h) compounds of Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Cr and / or Bi as
  • Component H and / or i) further auxiliaries and additives as component I.
  • These compositions are particularly suitable for pickling or passivating, in particular phosphating or as a rust converter for the metal surfaces mentioned in the present application.
  • compositions according to the invention can contain at least one corrosion inhibitor.
  • Suitable corrosion inhibitors are selected from the group consisting of butynediol, benzotriazole, aldehydes, aminocarboxylates, amino- and nitrophenols, amino alcohols, aminobenzimidazole, aminoimidazolines, aminotriazole, benzimidazolamines, benzothiazoles, derivatives of benzotriazole and various boranol acid esters, such as boramate aminolates, such as boronic acid amines with carbonic acid esters such as boramate aminates, such as boramate aminates, such as boramate aminates, with boric acid aminates such as boronic acid amines, such as boric acid amines, such as boramic acid esters with boric acid amines such as, , Quinoline derivatives, dibenzyl sulfoxide, dicarboxylic acids and their esters, diisobuten
  • butynediol and benzotriazole in particular in the surface treatment of copper
  • compounds structurally related to benzotriazole such as tolyltriazole and benzotriazole carboxylic acid.
  • polymers G ' built up from ga) at least one polymer containing amino groups as component G'a gb) at least one aromatic compound as component G "b, which is a phenol or a quinone or has a phenolic or quinoid structural unit; gc) optionally an aldehyde as component G'c.
  • Component G ' is a polymer composed of at least one polymer containing amino groups as component G'a and at least one aromatic compound as component G * b, which is a phenol or quinone or has a phenolic or quinoid structural unit. If necessary, the polymer contains as component G'c a building block resulting from a reaction with an aldehyde.
  • polymers are to be understood as meaning those compounds which have at least three repeating units, preferably more than 10 repeating units.
  • the weight average molecular weight of the polymers used according to the invention is generally 500 to 5,000,000 g / mol, preferably 1000 to 1,500,000 g / mol.
  • the polymer can also be crosslinked, so that no molecular weight can be given, although the polymer can be dispersed, emulsified or suspended in customary industrial solvents.
  • Component G'a is a polymer containing amino groups.
  • Polymers used with preference are polyethylemmin, polyvinylamine, poly (vinylformamide-co-vinylamine), polylysine and polyaminostyrene.
  • Derivatives of polyamines which also have amino groups are also suitable, for example the reaction products of polyamines with carboxylic acids or sulfonic acids or carboxymethylation products of polyamines.
  • Further suitable and particularly preferred polymers are derivatives of polycarboxylates containing amino groups, in particular the reaction products of diamines and copolymers which contain repeat units of maleic acid, acrylic acid or methacrylic acid, such as the reaction products of styrene-maleic anhydride copolymers
  • R is an organic radical, preferably an alkylene, cycloalkylene, arylene, arylalkylene or alkylarylene radical. This residue can be interrupted by heteroatoms or can be substituted as desired, suitable substituents being alkyl, alkenyl, aryl,
  • R is preferably a C 2 . 32 - alkylene radical, particularly preferably a C 2 . 1 -alkylene radical, which can be interrupted by heteroatoms selected from -N- and -O- and C ⁇ _ 6 -alkyl radicals or heteroatom-containing groups, for example amino groups, can carry.
  • Particularly preferred radicals are ethyl, n-butyl and n-hexyl radicals.
  • R ', R "and R'” independently of one another denote hydrogen or any organic radicals.
  • Suitable organic radicals are generally alkyl, cycloalkyl, alkenyl, aryl, alkylaryl and arylalkyl radicals, which can optionally be interrupted by heteroatoms or substituted with heteroatom-containing groups.
  • R ', R "and R"' are independently hydrogen or hydrocarbyl, more preferably hydrogen, C ⁇ - 6 alkyl, C 6 - 10 aryl, very particularly preferably methyl, ethyl, i-propyl, n-propyl, phenyl ,
  • polymers containing amino groups are commercially available (polyethyleneimine, polyvinylamine) or can be prepared by methods known to those skilled in the art. Suitable processes for the production of polyvinylamine are e.g. in EP-A 216 387, DE-A 38 42 820, DE-A 195 266 26, DE-A 195 159 43.
  • the polymers of the formulas (X) and (XI) used with particular preference can be prepared, for example, according to the process disclosed in US Pat. No. 4,046,748.
  • the polymers containing amino groups are generally in desalted form.
  • the degree of hydrolysis is generally from 0.5 to 100%, preferably from 50 to 100%.
  • Component G'b is a phenol or quinone or a compound which has a phenolic or quinoid structural unit.
  • Suitable quinones or quinone derivatives are generally systems derived from o-benzoquinone or from p-benzoquinone. Systems derived from p-benzoquinone are preferably used.
  • Compounds of the general formula (VII) are particularly preferred:
  • R 1 , R 2 , R 3 and R 4 can independently be hydrogen, alkyl, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl radicals.
  • R 1 to R 4 are preferably independently of one another hydrogen or C 1 -C 1 -alkyl radicals, C 2 - to C 1 -alkenyl radicals, C 6 - to C 1 -aryl radicals or C 5 - to C 16 -cycloalkyl radicals. It is also possible that R 1 and R 2 and / or R 3 and R 4 each together form a cyclic radical which can be saturated or unsaturated.
  • This cyclic radical is preferably a cycle of a total of six carbon atoms, two carbon atoms originating from the basic structure in formula (VII).
  • the radicals mentioned can in turn be substituted by alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl radicals or interrupted by heteroatoms or substituted by heteroatom-containing groups.
  • the radicals R 1 to R 4 in formula (VII) are particularly preferably independently of one another hydrogen and methyl.
  • Compounds of the formula (VE) used with particular preference are selected from the group consisting of benzoquinone, 2,3,5-trimethylbenzoquinone, 2,6-dimethylbenzoquinone, naphthoquinone and anthraquinone.
  • Suitable phenols or compounds which have a phenolic or quinoid structural unit are compounds of the general formula (VIII):
  • radicals R 5 , R 6 , R 7 , R 8 and R 9 independently of one another have the meaning given for R 1 to R 4 . Furthermore, the radicals R 5 and R 6 , or R 6 and R 7 , or R 7 and R 8 , or R 8 and R 9 together can form a cyclic radical, as is the case for R 1 and R 2 or R 3 and R 4 is defined. Furthermore, one or two of the radicals R 5 to R 9 can be -OM.
  • M in formula (VIII) represents hydrogen or a cation.
  • M + is an alkali metal cation, preferably a sodium or potassium ion.
  • ⁇ is a divalent or polyvalent cation, preferably an alkaline earth metal cation or Zn, Mn or Cr (III), particularly preferably magnesium or calcium.
  • R 5 to R 9 can also be - SO ⁇ M “1" , - NO, halogen, - COOTV ⁇ , -C (O) R “" (where R “" is hydrogen, an alkyl, aryl, , Cycloalkyl, aralkyl or alkaryl radical), -N (R “") 2 , -OR “” or -SH or other functional groups which are known to the person skilled in the art. In general, only one of the radicals R 5 to R 9 has one of the latter meanings.
  • Preferred compounds of the formula (VIII) are 1-, 2- or 3-valent phenols which can be substituted by the radicals mentioned above. In addition to the phenolic compounds mentioned, their salts are also suitable.
  • Particularly preferred compounds of formula (VIII) are phenol, 4,4'-dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfoxide, phenolsulfonic acid, 1,4-dihyroxynaphthalene, nitrophenol, (N, N-dimethylamino) -l-phenol, hydroxythioanisole, pyrogallol, phloroglucinol, 1, 2,4-trihydroxybenzene, 2,2 ', 4,4'-tetrahydroxybenzophenone, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, trihydroxybenzoic acids such as gallic acid, alkyl salicylates such as ethyl salicylate, Alkyl 3,4-dihydroxybenzoates such as ethyl 3,4-dihydroxybenzoate, alkyl gallates such as propyl gallate, 2,3-di
  • Phenol and pyrocatechol are particularly preferably used.
  • the polymer (component G ') is optionally composed of an aldehyde as a further component, component G'c.
  • This additional component is present, for example, when the polymer is produced by a Mannich reaction.
  • all aldehydes are suitable as component G'c.
  • Aldehydes of the formula (LX) are preferably used.
  • R 10 denotes hydrogen, alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkaryl.
  • R 10 is preferably hydrogen, Ci - 14 - alkyl, Ci _ 1 - alkenyl, C 5 - 16 - cycloalkyl, C 6 - 14 - aryl, C - 14 - aralkyl or C - 1 8 - alkaryl.
  • R 10 can be substituted by heteroatom-containing radicals selected from the group consisting of halogen, preferably chlorine or bromine, NO 2 , SH, OH, acetyl, carboxyl, (-C (O) -phenyl) or interrupted by heteroatoms.
  • the radical R 10 can in turn itself be substituted with alkyl, cycloalkyl, aryl, alkaryl or aralkyl radicals, which in turn can carry heteroatom-containing groups or whose chain or cycle can be interrupted by heteroatoms.
  • At least one component is particularly preferably selected from the group consisting of formaldehyde, ethanal, propanal, butanal, citronellal, benzaldehyde, 2-chlorobenzaldehyde, 2-hydroxybenzaldehyde, 2-propenal, 3,3-dimethyl-acrolein, 4 -Methylbenzaldehyde, 4- (l, l-dimethylethyl) benzaldehyde, anisaldehyde, 4-chloro-benzaldehyde, 3-hydroxy-2,2-dimethyl-propanal, 7-hydroxy-3,7-dimethyl-octanal, N-hexanal , 2-furfural, 3-methyl-4-oxo-2-butenoic acid methyl ester, 3-methylbutanal, 2-ethylhexanal, 2-methylpropanal, 2-phenylpropionaldehyde, 3,7-dimethylocta-2,
  • the polymers (component G ') can be prepared by methods known to those skilled in the art. Polymers obtained by the Michael reaction (Rl) and those obtained by adding a suitable aldehyde (component Ic) in the sense of a Mannich reaction (R2) are preferred. The following shows a Michael reaction (Rl) using the example of benzoquinone:
  • R 11 here denotes hydrogen or an organic radical, depending on the polymer containing amino groups used (component Ia).
  • R ⁇ is preferably hydrogen or methyl.
  • compositions according to the invention may contain a corrosion inhibitor G "):
  • Component G is at least one polymer composed of the structural element (1)
  • R ' is hydrogen, an alkyl, cycloalkyl, aryl, aralkyl or alkaryl radical with less than 31 carbon atoms, which may optionally be substituted by alkyl radicals or heteroatom-containing groups, preferably chloro, hydroxyl or amino groups, or by heteroatoms Nitrogen or oxygen, may be interrupted or contain double bonds; preferably, R 'is hydrogen or C 1 - 6 - alkyl, C 1-6 - hydroxyalkyl, C ⁇ ö aminoalkyl or C. 6 10- aryl, in structural element (3)
  • R "and R '" are any radicals with a molecular weight of ⁇ 200 g / mol, preferably independently of one another hydrogen, alkyl, cycloalkyl, aryl, aralkyl or alkaryl radicals, particularly preferably hydrogen or C ⁇ - 6 - alkyl or C 6 _ 10 aryl residues, in structural element (2), (3) and (4)
  • M each independently represents hydrogen or a cation, preferably an alkali metal cation, particularly preferably a sodium or potassium ion, or a divalent or polyvalent cation, preferably an alkaline earth metal cation or Zn, Zr, Cr, Mn, Fe, Co, Ni, Cu, Al , Ce, V, particularly preferably magnesium, calcium, zinc or manganese, if there are sufficient negative charges to be compensated, and in structural element (5)
  • R is hydrogen, an alkyl, cycloalkyl, aryl, aralkyl or alkaryl radical which can optionally be substituted by alkyl radicals or heteroatom-containing groups, preferably chloro, hydroxyl or amino groups, or can be interrupted by heteroatoms, preferably nitrogen or oxygen ; preferably R is hydrogen or C ⁇ - 6 - alkyl, Ci ⁇ hydroxyalkyl, C ⁇ -Arriinoalkyl or C 6 - ⁇ o-aryl.
  • the weight average molecular weight of the polymers used is generally> 500 g / mol, preferably 1000 to 1,500,000 g / mol.
  • the polymers (component G ”) preferably have the following elemental composition:
  • C 20-82% by weight, preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight, H: 2.3-12.5% by weight, preferably 2.3 to 8% by weight, particularly preferably 2.5 to 5.5% by weight, N: 1-61% by weight, preferably 1 to 20% by weight, particularly preferably 1 to 15% by weight, O: 2-50% by weight, preferably 5 to 50 wt.%, particularly preferably 20 to 45 wt.%, S: 0-18.5 wt.%, preferably 0.5 to 18.5 wt.%, particularly preferably 5 to 15 wt.%, X : 0- ⁇ 46% by weight, preferably 0 to 38% by weight, particularly preferably 1 to 13% by weight, where X denotes any chemical element, preferably one or more of the cations mentioned for M.
  • Component G " is produced in any manner. Suitable processes are known to the person skilled in the art. In a particularly preferred embodiment, component G" is produced by polycondensation. Suitable process conditions for polycondensation are known to the person skilled in the art from the production of phenolic resins, urea resins and melamine resins, which are described, for example, in ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, SIXTH EDITION, 2000 ELECTRONIC RELEASE, chapter “Phenolic Resins", paragraphs 3 and 4 and in US Pat. No. 4,252,938 US 4,677,159 is disclosed.
  • component G by polycondensation, the following components are generally reacted with one another: a) at least one aldehyde as component G" a, b) at least one aromatic compound which carries at least one OM group or one sulfonic acid group, -SO 2 OM, or both groups, as component G "b, c) optionally at least one compound selected from diphenols or polyphenols with vicinal OM groups, where the vicinal OH groups can optionally be protected as acetal or ketal, as component G "c, in which component G" b and G "c M each independently of one another are hydrogen or a cation, preferably an alkali metal cation, particularly preferably a sodium or potassium ion mean, or a divalent or polyvalent cation, preferably an alkaline earth metal cation or Zn, Zr, Cr, Mn, Fe, Co, Ni, Cu, Al, Ce, V, particularly preferably magnesium, calcium, zinc or manga
  • the polycondensation can take place in the presence of a catalyst.
  • Suitable catalysts are known to the person skilled in the art.
  • a catalyst selected from the group consisting of acids, preferably mineral acids and oxalic acid, and bases, preferably alkali or alkaline earth metal hydroxides, and salts of weak acids and bases is preferably used.
  • the corrosion inhibitors if they are used at all in the compositions, are used in an amount of generally 0.01 to 50 g / 1, preferably 0.1 to 20 g / 1, particularly preferably 1 to 10 g / 1.
  • Component H In addition to or optionally instead of the components mentioned, compounds of Ce, Ni, Co, V, Fe, Zn, Zr, Ca, Mn, Mo, W, Cr and / or Bi can also be used.
  • the compositions according to the invention are preferably free of Cr (VI). If the compounds mentioned (component H) are nevertheless used, compounds selected from Fe, Zn, Zr and Ca are preferably used.
  • the amount of these compounds in the compositions according to the invention is - if these compounds are present at all - generally 0.01 to 100 g / 1, preferably 0.1 to 50 g / 1, particularly preferably 1 to 20 g / 1.
  • the compositions according to the invention can contain further auxiliaries * and additives.
  • auxiliaries and additives include conductivity pigments or conductive fillers, for example iron phosphide, vanadium carbide, titanium nitride, carbon black, graphite, molybdenum disulfide or barium sulfate doped with tin or antimony, with iron phosphide being preferred.
  • Such conductivity pigments or conductive fillers are added to the compositions according to the invention in order to improve the weldability of the metal surfaces to be treated or to improve a subsequent coating with electrocoat materials.
  • silica suspensions can be used, particularly when the compositions are used to treat aluminum-containing surfaces.
  • additives are generally in finely divided form, i.e. their average particle diameters are generally 0.005 to 5 ⁇ m, preferably 0.05 to 2.5 ⁇ m.
  • the amount of auxiliaries and additives is generally 0.1 to 50% by weight, preferably 2 to 35% by weight, based on the total mass of the compositions according to the invention.
  • compositions according to the invention may also contain additives to improve the forming behavior, for example wax-based derivatives based on natural or synthetic waxes, for example waxes based on acrylic acid, polyethylene, polytetrafluoroethylene (PTFE) waxes or wax derivatives or paraffins and their oxidation products.
  • PTFE polytetrafluoroethylene
  • the compositions according to the invention 'polymer dispersions based on styrene, 4-hydroxystyrene, contain butadiene, acrylic acid, Acrylklareestern, acrylamides, acrylates, methacrylic acid, methacrylic esters, methacrylamides, methacrylates, and derivatives of acrylamide.
  • the compositions according to the invention may also contain polyurethane dispersions and polyester urethane dispersions or polyurea dispersions.
  • compositions according to the invention are polyethylene glycols, polypropylene glycols, copolymers of ethylene oxide and copolymers of propylene oxide.
  • compositions according to the invention can additionally contain epoxy resins and / or condensation resins of the formaldehyde with phenol, urea, melamine, phenolsulfonic acid or naphthalenesulfonic acid.
  • compositions according to the invention when used in rust converters, they can additionally contain polyvinyl butyral.
  • compositions according to the invention containing component A can be used in all applications for surface treatment of metals, in particular in those applications in which the corrosion of metal surfaces can be a problem.
  • examples of such applications are paint stripping, metal pickling, electropolishing, chemical deburring, chemical and electrochemical metal deposition (in particular of Cu, Ni, Pd, Zn, Co, Mn, Fe, Mg, Sn, Pb, Bi, Ag, Au and their alloys), Conversion layer formation (in particular no-rinse conversion layer formation, i.e.
  • the type of application corresponds to technically customary methods with the addition that the compositions according to the invention are used together with other components which are technically customary for the corresponding application, or that they are brought into contact with the metal in additional treatment steps, such as spraying, dipping, painting or electro-painting using suitable formulations of the Corrosion-inhibiting compositions according to the invention, such as solutions, emulsions, dispersions, suspensions or aerosols.
  • compositions for metal deposition on metal or plastic surfaces comprising, in addition to components A, B and optionally C, and F:
  • component J optionally at least one acid or an alkali metal or alkaline earth metal salt of the corresponding acid as component J, and k) optionally further additives as component K.
  • compositions according to the invention are particularly suitable for the deposition of metals or metal alloys on metal or plastic surfaces. Suitable metal surfaces have already been mentioned above.
  • the deposition of metals or metal alloys on plastic surfaces is preferably carried out in the manufacture of printed circuit boards.
  • the deposition is preferably carried out in a chemical or electrochemical process.
  • compositions according to the invention may optionally further comprise at least one acid or an alkali metal or alkaline earth metal salt of the corresponding acid, preferably selected from the group consisting of HNO 3 , H 2 SO 4 , H 3 PO 4 , formic acid and acetic acid.
  • the acid is generally used in an amount of 0.5 to 700 g / 1, preferably 5 to 200 g / 1.
  • compositions according to the invention can contain further additives, which can vary depending on the intended use, the metal to be deposited, the objective and the process used.
  • Suitable additives are l- (2-methylpyridinium) -2-ethylsulfobetaine, l, l-dimethyl-2-propyl-l-amine, 1-pyridinium-2-ethylsulfobetaine, 1-pyridim ' um-2-hydroxy-3 propylsulfobetaine, 1-pyridinium-3-propylsulfobetaine, 2,2'-dichlorodiethyl ether, 2,5-dimethyl-3-hexyne-2,5-diol, 2-butyne-l, 4-diol, 2-butyne-l, 4-diol ethoxylate, 2-butyne-l, 4-diol propoxylate, 3- (2-ber ⁇ zothiazolylthio) -l-prop
  • Methylamido sulfonic acid N, N, N ', N'-tetiakis (2-hydroxypropyl) ethylenediamine, N, N-diethyl-2-propyne-1-amine, N, N-diethyl-4-amino-2-butyne 1 -ol, N, N-dimethyl-2-propyne-1-amine, N-2-ethylhexyl-3-aminosulfopropionic acid, N-allylpyridinium chloride, sodium salt of sulfated alkylphenol ethoxylates, sodium 2-ethylhexyl sulfate, nicotinic acid, nitrilotriacetic acid and salts derived therefrom , Nitrobenzenesulfonic acid Na salt, N-methallylpyridinium chloride, ortho-chlorobenzaldehyde, phosphonium salts, phthalic acid amides, picolinic acid
  • Naphtholethoxylat ß-Naphtholethoxylatsulfat Na salt
  • sulfonium salts sulfonic acids such as methanesulfonic acid, thiodiglycol, Thiodiglykolethoxylat, thioethers, thio - ureas, thiuram disulfides, vinylsulfonic acid sodium salt, cinnamic acid and its derivatives, zinc phosphates and silicates, zirconium phosphates and silicates, hypophosphites (e.g.
  • sodium hypophosphite NaBH 4
  • dimethylaminoborane diethylaminoborane
  • hydrazine formaldehyde
  • HFx HFx
  • borate borate
  • urotrophin 3 polyethylene glycols with molecular weight 100-1000000 g / mol
  • block copolymers of ethylene oxide and propylene oxide for example Pluronic brands from BASF Aktiengesellschaft, Ludwigshafen / Rh.
  • statistical copolymers of ethylene oxide and propylene oxide in particular with molecular weights in the range 100-2000 g / mol.
  • compositions according to the invention in accordance with this embodiment, metal deposits in particular are possible by electrochemical or chemical means. Whether an electrochemical or chemical deposition is carried out depends on the metal, the metal surface and the desired result.
  • the present application further relates to a process for the surface treatment of metals, the metal surface being brought into contact with a polymer (component A) comprising at least one structural unit of the formula (I)
  • this structural unit can be part of the main polymer chain or can be bonded to a main polymer chain via an anchor group
  • M is hydrogen or an ammonium or metal cation.
  • Suitable methods are e.g. Paint stripping, metal pickling, electropolishing, chemical deburring, chemical and electrochemical metal deposition, conversion layer formation (in particular no-rinse conversion layer formation), corrosion protection (in particular on copper, for example in the manufacture of printed circuit boards and on steel), lubrication and greasing (in particular in cold forming ).
  • the polymer can be present in solution, emulsion, suspension or aerosol.
  • the polymer (component A) is preferably present in one of the above-mentioned compositions according to the invention.
  • the type of application corresponds to technically customary methods with the addition that the polymers (component A) used according to the invention are used together with other components technically customary for the corresponding application or that they are brought into contact with the metal in additional treatment steps, such as spraying , Dipping, painting or electro-painting using suitable formulations of the polymers.
  • a metal surface is brought into contact with a composition which has components A, B and optionally C, and also D and / or E, or with a composition which, in addition to components A, B and optionally C , and D and / or E as further components having components G and / or H and / or I.
  • Suitable components B to I are listed above.
  • pickling or passivation in particular phosphating of the metal surface, is preferably carried out. Suitable process steps and devices for passivation, in particular phosphating or for pickling metal surfaces, are known to the person skilled in the art.
  • the metal surfaces are treated, in particular passivation, particularly preferably phosphating or pickling, by spraying a composition according to the invention on the metal surface or dipping the metal surface into a composition according to the invention, depending on the number, size and shape of the parts to be treated.
  • compositions according to the invention containing phosphoric acid as component E can be applied by a “roll-on” or “dry-in-place ⁇ ” or “no-rinse” method, the phosphating composition according to the invention is applied to the metal strip and dried without rinsing, a polymer film being formed.
  • Another object of the present application is a method comprising the steps: a) optionally cleaning the metal surface to remove oils, fats and dirt, b) optionally washing with water, c) optionally pickling to remove rust or other oxides, optionally in Presence of the polymer used according to the invention (component A), d) optionally washing with water, e) treatment of the metal surface in the presence of the polymer used according to the invention (component A), f) optionally washing with water, g) optionally aftertreatment.
  • the treatment of the metal surface in step e) can be passivation, in particular phosphating, by methods known to the person skilled in the art.
  • a protective layer, film or impregnation is applied to the metal. If phosphating is carried out in step e), post-treatment of the metal surface in step g) with passivating additives is possible.
  • washing with water takes place between the individual process steps in order to avoid contamination of the solution required for the respective subsequent step with components of the solution used in the previous step.
  • the method according to the invention as a “no rinse method”, that is to say without steps b), d) and f).
  • the steps of cleaning (step a)) and treating the metal surface in the presence of the polymer used according to the invention (component A), preferably passivation (step e)) can also be carried out in one step, ie with a formulation which, in addition to the customary ones Detergents also contains the composition according to the invention.
  • the metal surface can be provided with a lacquer.
  • the painting is also carried out by methods known to those skilled in the art.
  • a further embodiment of the present application relates to a method for the deposition of metals or metal alloys on a metal or plastic surface, the metal or plastic surface being brought into contact with a polymer (component A) comprising at least one structural unit of the formula (I)
  • this structural unit can be part of the main polymer chain or can be bonded to a main polymer chain via an anchor group
  • M is hydrogen or an ammonium or metal cation.
  • the metal or plastic surface is preferably brought into contact with a composition which contains components A, B and optionally C and F, or with a composition which is in addition to components A, B and optionally C and F as further components the components J optionally contains K.
  • a composition which contains components A, B and optionally C and F or with a composition which is in addition to components A, B and optionally C and F as further components the components J optionally contains K.
  • Suitable components A, B, C, F, J, K have already been mentioned above.
  • a deposition of metals or metal alloys on a plastic surface is generally in the case of plastic metallization, in particular in the case of. Manufacture of everyday objects or printed circuit boards. Examples are copper plating or nickel plating of circuit boards without external current or Articles of daily use with a plastic surface, with a nickel plating and then a chrome plating following the copper plating and a chrome plating following the nickel plating.
  • the deposition of metals or metal alloys on metal or plastic surfaces takes place in a particularly preferred embodiment in each case without external current (also called chemically) or electrolytically.
  • external current also called chemically
  • electrolytically Such methods are known to the person skilled in the art.
  • Chemical or electrochemical gold deposition, chemical or electrochemical copper deposition, chemical or electrochemical nickel deposition, chemical palladium deposition, electrochemical zinc deposition, electrochemical tin deposition are particularly preferably carried out in the process according to the invention.
  • the processes mentioned also include their alloys with other elements; CuZn, CuSn, CuNi, SnPb, SnAgBiCu, SnAgCu, SnBi, SnAg, SnCu, NiPd, NiP, ZnFe, ZnNi, ZnCo, ZnMn are particularly preferred, the components of the alloy mentioned being able to be contained in the alloy in any concentration.
  • Processes are also in accordance with the invention in which conductive polymers are deposited, these being considered in the broadest sense as metals.
  • One such conductive polymer is polypyrrole.
  • Further embodiments of the process according to the invention are, for example, cleaning, etching, glossing and pickling processes, in which, in addition to the use of component A according to the invention, acids, oxidizing agents and corrosion inhibitors as well as dissolved metal salts are used, and processes for the production of printed circuit boards in which compositions containing the Component A can be used both for the metallization of the printed circuit board including the holes contained therein as well as for surface treatment of the printed circuit board.
  • Compositions containing component A can be used on the one hand in the surface treatment of metals present on the printed circuit board, for example with the aim of protecting against corrosion or in improving the solderability, as well as in processes in which non-conductive surfaces are used as part of the metal deposition with the Compositions used according to the invention containing component A are treated, for example with the aim of through-contacting printed circuit boards.
  • the present application further relates to the use of polymers (component A) comprising at least one structural unit of the formula (I)
  • this structural unit can be part of the main polymer chain or can be bonded to a main polymer chain via an anchor group
  • M is hydrogen or an ammonium or metal cation
  • Printed circuit boards that have been pretreated using standard technical processes are mixed in a mixture of 10 ml of a solution X, 10 ml of a solution Y and 80 ml of water coppers.
  • the composition of the solutions is as follows: Solution X: 9g CuSO 4 x 5 H 2 O 27.5g formaldehyde (36.5%)
  • the carboxymethylated polyethyleneimine has an average molecular weight of 50,000 g / mol (determined by light scattering) and was prepared from polyethyleneimine analogously to Example 1 in WO 97/40087, the degree of carboxymethylation being 80 mol%.
  • the mixture of solution X, solution Y and water has a higher stability than a comparable mixture which contains EDTA as complexing agent instead of carboxymethylated polyethyleneimine.
  • the stability was determined quantitatively from the amount of copper deposited when no substrate was immersed in the bath. The more Cu is deposited in a bath without a substrate, the lower its stability. The amount of copper deposited under comparable conditions is at least 5% less than in technically usual baths.
  • a galvanic bath of the following composition is used for electrochemical copper deposition on glass fiber reinforced epoxy resin at 50 ° C. and a current density of 2 A / dm 2 : 18 g / 1 copper, as copper sulfamate
  • a bath of the following composition is used for chemical nickel deposition on glass fiber reinforced epoxy resin at 90 ° C:
  • galvanic baths of the following composition are used:
  • Example 5 Electrochemical gold deposition A galvanic bath of the following composition is used for electrochemical gold deposition on glass fiber reinforced epoxy resin at 35 ° C and a current density of 1 A / dm 2 :
  • Example 6 Electrolytic cleaning of mild steel
  • a bath of the following composition is used for the surface treatment of stainless steel.
  • the workpiece is switched as cathode for 5 minutes at room temperature, with a current density of 1 A / dm 2 .
  • a bath of the following composition is used for the surface treatment of copper.
  • the workpiece is used as a cathode for 1 minute at room temperature

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP03760658A 2002-06-19 2003-06-18 Komplexbildner f r die behandlung von metall- und kunststoff oberfl chen Withdrawn EP1525247A2 (de)

Applications Claiming Priority (3)

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DE2002127362 DE10227362A1 (de) 2002-06-19 2002-06-19 Komplexbildner für die Behandlung von Metall- und Kunstoffoberflächen
DE10227362 2002-06-19
PCT/EP2003/006491 WO2004001099A2 (de) 2002-06-19 2003-06-18 Komplexbildner für die behandlung von metall- und kunststoffoberflächen

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AU (1) AU2003246562A1 (enrdf_load_stackoverflow)
CA (1) CA2489916A1 (enrdf_load_stackoverflow)
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US20050209117A1 (en) 2005-09-22
DE10227362A1 (de) 2004-01-08
CA2489916A1 (en) 2003-12-31
AU2003246562A1 (en) 2004-01-06
JP2005536579A (ja) 2005-12-02
WO2004001099A2 (de) 2003-12-31
AU2003246562A8 (en) 2004-01-06

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